The present invention relates to selected 4-aminobut-2-ynecarboxylic acid derivatives, to the preparation of such compounds, to the use of such compounds in the antimicrobial treatment of surfaces, as antimicrobial active ingredients against gram-positive and gram-negative bacteria, yeasts and fungi and in preserving cosmetics, household products, textiles, plastics and for use in disinfectants.
The compounds according to the invention correspond to the formula 
wherein
R1 and R2 are each independently of the other hydrogen, C1-C20alkyl; C3-C12cycloalkyl; unsubstituted or C1-C5alkyl-, C3-C12cycloalkyl-, C1-C5alkoxy-, C3-C12cycloalkoxy-, halo-, oxo-, carboxy-, carboxy-C1-C7alkyl ester-, carboxy-C3-C12cycloalkyl ester-, cyano-, trifluoromethyl-, pentafluoroethyl-, amino-, N,N-mono- or di-C1-C20alkylamino- or nitro-substituted phenyl, phenyl-C1-C5alkyl, naphthyl or naphthyl-C1-C5alkyl,
R3 is hydrogen; C1-C20alkyl; or C3-C12cycloalkyl; there not being included compounds of formula (1) wherein
a) R1 and R2 are each independently of the other C1-C3alkyl; and
R3 is hydrogen; and
b) R1 is methyl;
R2 is phenyl; or chloro-substituted phenyl; and
R3 is hydrogen, methyl or ethyl.
The invention preferably relates to compounds of formula (1) wherein
R1 and R2 are each independently of the other hydrogen; C1-C20alkyl; C1-C5alkoxy; unsubstituted or C1-C5alkyl- or halo-substituted phenyl or phenyl-C1-C5alkyl; and
R3 is hydrogen; or C1-C5alkyl;
and especially to compounds of formula (1) wherein
R1 and R2 are each independently of the other hydrogen; C1-C20alkyl; C1-C5alkoxy; unsubstituted or C1-C5alkyl- or halo-substituted phenyl; and
R3 is hydrogen; or C1-C5alkyl.
Special preference is given to compounds of formula (1) wherein
R1 is C2-C20alkyl; C3-C12cycloalkyl; unsubstituted or C1-C5alkyl-, C3-C12cycloalkyl-, C1-C5-alkoxy-, C3-C12cycloalkoxy-, halo-, oxo-, carboxy-, carboxy-C1-C7alkyl ester-, carboxy-C3-C12cycloalkyl ester-, cyano-, trifluoromethyl-, pentafluoroethyl-, amino-, N,N-mono- or di-C1-C20alkylamino- or nitro-substituted phenyl, phenyl-C1-C5alkyl, naphthyl or naphthyl-C1-C5alkyl;
R2 is unsubstituted or C1-C5alkyl-, C3-C12cycloalkyl-, C1-C5alkoxy-, C3-C12cycloakloxy-, halo-, oxo-, carboxy-, carboxy-C1-C7alkyl ester-, carboxy-C3-C12cycloalkyl ester-, cyano-, trifluoromethyl-, pentafluoroethyl-, amino-, N,N-mono- or di-C1-C20alkylamino- or nitro-substituted phenyl, phenyl-C1-C5alkyl, naphthyl or naphthyl-C1-C5alkyl; and
R3 is hydrogen; C1-C20alkyl; or C3-C12cycloalkyl.
Special preference is given to compounds of formula (1) wherein
R1 is C2-C20alkyl; and
R2 is unsubstituted or C1-C5alkyl-, C1-C5alkoxy-, halo-, trifluoromethyl- or pentafluoroethyl-substitute phenyl,
and especially to compounds of formula (1) wherein
R1 and R2 are each independently of the other hydrogen; or C4-C20alkyl.
Examples of especially preferred compounds according to the invention correspond to the formulae 
The 4-aminobut-2-ynecarboxylic acid derivatives according to the invention are prepared in a manner known per se by reacting an amine compound of formula (5) with propargyl bromide and, in a second reaction step, reacting the metallized acetylene with chloroformic acid esters or CO2 in accordance with the following Reaction scheme: 
In that Reaction scheme
R1 and R2 are each independently of the other hydrogen, C1-C20alkyl; C3-C12cycloalkyl; unsubstituted or C1-C5alkyl-, C3-C12cycloalkyl-, C1-C5alkoxy-, C3-C12cycloalkoxy-, halo-, oxo-, carboxy-, carboxy-C1-C7alkyl ester-, carboxy-C3-C12cycloalkyl ester-, cyano-, triflutrifluoromethyl-, pentafluoroethyl-, amino-, N,N-mono- or di-C1-C20alkylamino- or nitro-substituted phenyl or phenyl-C1-C5alkyl, naphthyl, naphthyl-C1-C5alkyl; and
R3 is hydrogen; C1-C20alkyl; or C3-C12cycloalkyl.
The invention relates also to the process for the preparation of the 4-aminobut-2-ynecarboxylic acid derivatives according to the invention.
The 4-aminobut-2-ynecarboxylic acid derivatives, according to the invention, of formula 
wherein
R1 and R2 are each independently of the other hydrogen, C1-C20alkyl; C3-C12cycloalkyl; unsubstituted or C1-C5alkyl-, C3-C12cycloalkyl-, C1-C5alkoxy-, C3-C12cycloalkoxy-, halo-, oxo-, carboxy-, carboxy-C1-C7alkyl ester-, carboxy-C3-C12cycloalkyl ester-, cyano-, trifluoromethyl-, pentafluoroethyl-, amino-, N,N-mono- or di-C1-C20alkylamino- or nitro-substituted phenyl, phenyl-C1-C5alkyl, naphthyl or naphthyl-C1-C5alkyl,
R3 is hydrogen; C1-C20alkyl; or C3-C12cycloalkyl; exhibit pronounced antimicrobial activity, especially against gram-positive and gram-negative bacteria and against bacteria of skin flora, and also against yeasts and moulds. They are accordingly suitable especially in the disinfection, deodorisation and general and antimicrobial treatment of the skin and mucosa and of integumentary appendages (hair), more especially in the disinfection of hands and of wounds.
They are therefore suitable as antimicrobial active ingredients and as preservatives in personal care preparations, for example shampoos, bath additives, hair-care products, liquid and solid soaps (based on synthetic surfactants and salts of saturated and/or unsaturated fatty acids), lotions and creams, deodorants, other aqueous or alcoholic solutions, e.g. cleansing solutions for the skin, moist cleansing cloths, oils or powders.
The invention accordingly relates also to a personal care preparation comprising at least one compound of formula (1) and cosmetically tolerable carriers or adjuvants.
The personal care preparation according to the invention comprises from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight, based on the total weight of the composition, of the compound of formula (1) and cosmetically tolerable adjuvants.
Depending upon the form of the personal care preparation, it will comprise, in addition to the 4-aminobut-2-ynecarboxylic acid derivative of formula (1), further constituents, for example sequestering agents, colourings, perfume oils, thickening or solidifying (consistency regulator) agents, emollients, UV absorbers, skin-protective agents, antioxidants, additives that improve mechanical properties, such as dicarboxylic acids and/or Al, Zn, Ca and Mg salts of C14-C22fatty acids, and optionally preservatives.
The personal care preparation according to the invention may be formulated as a water-in-oil or oil-in-water emulsion, as an alcoholic or alcohol-containing formulation, as a vesicular dispersion of an ionic or non-ionic amphiphilic lipid, as a gel, a solid stick or as an aerosol formulation.
As a water-in-oil or oil-in-water emulsion the cosmetically tolerable adjuvant preferably comprises from 5 to 50% of an oily phase, from 5 to 20% of an emulsifier and from 30 to 90% water. The oily phase may contain any oil suitable for cosmetic formulations, e.g. one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, a fatty acid ester or a fatty alcohol. Preferred mono- or poly-ols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
Cosmetic formulations according to the invention are used in various fields. For example, the following preparations especially come into consideration:
skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, synthetic detergents or washing pastes,
bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts;
skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils;
cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipstick, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish remover, nail hardeners, or cuticle removers;
intimate hygiene preparations, e.g. intimate washing lotions or intimate sprays;
foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callous-removing preparations;
light-protective preparations, such as sun milks, lotions, creams, oils, sun blocks or tropicals, pre-tanning preparations or after-sun preparations;
skin-tanning preparations, e.g. self-tanning creams;
depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations;
insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks;
deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons;
antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;
preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks;
hair-removal preparations in chemical form (depilation), e.g. hair-removing powders, liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams;
shaving preparations, e.g. shaving soap, foam shaving creams, non-foaming shaving creams, foams, gels, preshave preparations for dry shaving, aftershaves or aftershave lotions;
fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams;
dental-care, denture-care and mouth-care preparations, e.g. toothpastes, gel tooth-pastes, tooth powders, mouthwash concentrates, anti-plaque mouthwashes, denture cleaners or denture fixatives;
cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pre-treatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hair sprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or camomile.
An antimicrobial soap has, for example, the following composition:
0.01 to 5% by weight of the compound of formula (1),
0.3 to 1% by weight titanium dioxide,
1 to 10% by weight stearic acid,
ad 100% soap base, e.g. the sodium salts of tallow fatty acid and coconut fatty acid or glycerols.
A shampoo has, for example, the following composition:
0.01 to 5% by weight of the compound of formula (1),
12.0% by weight sodium laureth-2-sulfate,
4.0% by weight cocamidopropyl betaine,
3.0% by weight NaCl and
water ad 100%.
A deodorant has, for example, the following composition:
0.01 to 5% by weight of the compound of formula (1),
60% by weight ethanol,
0.3% by weight perfume oil, and
water ad 100%.
The invention relates also to an oral composition, comprising
0.01 to 15% by weight, based on the total weight of the composition, of the compound of formula (1) and orally tolerable adjuvants.
Example of an oral composition:
10% by weight sorbitol,
10% by weight glycerol,
15% by weight ethanol,
15% by weight propylene glycol,
0.5% by weight sodium lauryl sulfate,
0.25% by weight sodium methylcocyl taurate,
0.25% by weight polyoxypropylene/polyoxyethylene block copolymer,
0.10% by weight peppermint flavouring,
0.1 to 0.5% by weight of a compound of formula (1), and
48.6% by weight water.
The oral composition according to the invention may be, for example, in the form of a gel, a paste, a cream or an aqueous preparation (mouthwash).
The oral composition according to the invention may also comprise compounds that release fluoride ions which are effective against the formation of caries, for example inorganic fluoride salts, e.g. sodium, potassium, ammonium or calcium fluoride, or organic fluoride salts, e.g. amine fluorides, which are known under the trade name Olafluor.
The 4-aminobut-2-ynecarboxylic acid derivatives of formula (1) according to the invention are also suitable for the treatment, especially preservation, of textile fibre materials. Such materials are undyed and dyed or printed fibre materials, e.g. of silk, wool, polyamide or polyurethanes, and especially cellulose-containing fibre materials of all kinds. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen, jute and hemp, as well as cellulose and regenerated cellulose. Preferred suitable textile fibre materials are made of cotton.
The 4-aminobut-2-ynecarboxylic acid derivatives according to the invention are also suitable for the treatment of plastics, especially for imparting antimicrobial properties to or preserving plastics, e.g. polyethylene, polypropylene, polyurethane, polyester, polyamide, polycarbonate, latex, etc. Fields of use therefor are, for example, floor coverings, plastics coatings, plastics container and packaging materials; kitchen and bathroom utensils (e.g. brushes, shower curtains; sponges, bathmats), latex, filter materials (air and water filters), plastics articles used in the field of medicine, e.g. dressing materials, syringes, catheters etc., so-called xe2x80x9cmedical devicesxe2x80x9d, gloves and mattresses.
Paper, for example papers used for hygiene purposes, may also be provided with antimicrobial properties using the 4-aminobut-2-ynecarboxylic acid derivatives according to the invention.
It is also possible for nonwovens, e.g. nappies/diapers, sanitary towels, panty liners, and cloths for hygiene and household uses, to be provided with antimicrobial properties in accordance with the invention.
The 4-aminobut-2-ynecarboxylic acid derivatives of formula (1) are also used in washing and cleaning formulations, e.g. in liquid and powder detergents or fabric conditioners.
The 4-aminobut-2-ynecarboxylic acid derivatives of formula (1) can be used especially also in household and all-purpose cleaners for cleaning and disinfecting hard surfaces.
A cleaning preparation has, for example, the following composition:
0.01 to 5% of the compound of formula (1)
3.0% octyl alcohol 4EO
1.3% fatty alcohol C8-C10polyglucoside
3.0% isopropanol
ad 100% water.
In addition to preserving cosmetics and household products, it is also possible for technical products to be preserved and provided with antimicrobial properties; use as a biocide in technical processes is also possible, for example in paper treatment, especially in paper treatment liquors, printing thickeners of starch or cellulose derivatives, varnishes and paints.
The 4-aminobut-2-ynecarboxylic acid derivatives of formula (1) are also suitable for the antimicrobial treatment of wood and for the antimicrobial treatment of leather, the preservation of leather and the finishing of leather with antimicrobial properties.
The compounds according to the invention are also suitable for the protection of cosmetic products and household products from microbial damage.
The following Examples serve to illustrate the present invention but do not limit it.